Note: Descriptions are shown in the official language in which they were submitted.
~2~3~9 62301-1391
BUILT NONAQUEOUS LIQUID NONIONIC L~UNDRY DETERGENT COMPOSITION
CONTAINING ~REA STABILI~ER AND METHOD~ OF USE
BACKGROUND OF THE INVENTION
(1) Field of Invention
This invention relates to nonaqueous liquid fabric
treating compositions. More particularly, this invention
relates to nonaqueous liquid laundry detergent compositions
which are stable against phase separation and gelation and are
easily pourable and to the use of these compositions for
cleaning soiled fabrics.
(2) Discussion of Prior Art
Liquid nonaqueous heavy du-ty laundry detergent
compositions are well known in the art. For instance,
compositions of that type may comprise a liquid nonionic
surfactant in which are dispersed particles of a builder, as
shown for instance in the U.S.P. Nos. 4,316,812, 3,630,929 and
~,264,466 and British Patent Nos. 1,205,711, 1,270,040 and
1,600,981.
The related Canadian applications assigned to the
common assignee are No. 498,815, filed December 31st, 1985; No.
478,380, filed April 4th, 1985; No. 478,379, filed April 4th,
1985; and No. 502,998, filed February 28th, 1986.
These applications are directed to liquid nonaqueous
nonionic laundry detergent compositions.
; Liquid detergents are often considered to be more
convenient to employ than dry powdered or particulate products
and, therefore, have found substantial favour with consumers.
They are readily measurable, speedily dissolved in the wash
water, capable of being easily applied in concentrated
solutions or dispersions to soi:led areas on garments to be
laundered and are non-dusting, and they usually occupy less
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~2~83~9 62301-1391
storage space. Additionally, the liquid detergents may have
incorporated in their :Eormu].ations materials which
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~!L2~;13389
could not stand drying operations without deterioration, which matèrials are
often desirably employed in the manufacture of particulate detergent
products. Although they are possessed of many advantages over unitary or
particulate solid products, liquid detergents often have certain inherent
disadvantsges too, which have to be overcome to produce acceptable
commercial detergent products. Thus, some such products separate out on
storage and others separate out on cooling and are not readily redispersed.
In some cases the product viscosity changes and it becomes either too thick
to pour or so thin as to appear watery. Some clear products become cloudy
and others gel on standing.
The present inventors have been involved in studying the behavior of
nonionic liquid surfactant systems with particulate matter suspended therein.
Of particular interest has been nonaqueous built laundry liquid detergent
compositions and the problem of settling of the suspended builder and other
laundry additives as well as the problem of gelling associated with nonionic
surfactants. These considerations have an impact on, for example, product
stability, pourability and dispersibility.
It is known that one of the major problems wlth built liquid laundry
detergents i8 their physical stability. This problem stems from the fact that
2~ the density o the solid particles dispersed in the nonionic liquid surfactant
is higher than the density of the liquid surfactant.
Therefore, the dispersed particles tend to settle out. Two basic
solutions exist to solve the settling out problem: increase nonionic liquid
viseosity and reduce the dispersed solid particle ~ize.
2 5 It is known that suspensions can be stabilized against settling by
adding inorganic or organic thickening agents or dispersants, such as, for
example, very high 3urface area inorganic materials, e. g. finely di~ided
silica , clays , etc ., organic thickeners , such as the cellulose ethers , acrylic
and acrylamide polymers, polyelectrolytes, etc. However, such increases in
suspension viscosity are naturally limited by the requirement that the liquid
- ~6~3~3~
suspension be readily pourable and flowable, even at low temperature.
Furthermore, these additives do not contribute to the cleaning performance
of the formulation.
Grinding to reduce the particle size provides the following advantages:
1. Specific surface area of the dispersed particles is increased, and,
therefore, particle wetting by the nonaqueous vehicle (liquid nonionic) i6
proportionately improved.
2. The average distance between dispersed particles i8 reduced with fl
proportionate increase in particle-to-particle interaction. Each of these
effects contributes to incresse the rest-gel strength and the suspension yield
stress while at the same time, grinding significantly reduces plastic
viscosity.
The yield stress is defined as the minimum stress necessary to induce a
plastic deformation (flow) of the suspension. Thus, visualizing the
suspension as a loose network of dispersed particles, if the applied stress is
lower than the yield stress, the suspension behaves like an elastic gel and
no plastic flow will occur. Once the yield stress is overcome, the network
breaks at some points and the sample begins to flow, but with a very high
apparent vi~cosity. If the shear stress is much higher than the yield
stress, the pigments are partially shear-deflocculated and the apparent
viscosity decreases. Einally, if the shear stress is much higher than the
yield stress value, the dispersed particles are completely shear-deflocculated
and the apparent viscosity is very low, as if no particle interaction were
present .
Therefore, the higher the yield stress of the suspension, the higher
the apparent viscosity at low shear rate and the better is the physical
stability against settling of the product.
In addition to the problem of settling or phase separation, the
nonaqueous liquid laundry detergents based Oll liquid nonionic sur~ctantæ
suffer from the drawback that the nonionics tend to gel when added to cold
126~313~
water. Thi~ is a particularly important problem in the ordinary use of
European household automatic washing machines where the user places the
laundry detergent composition in a dispensing unit (e. g. a dispensing
drawer) of the machine. During the operation of the machine the detergent
in the dispenser is subjected to a stream of cold water to transfer it to the
main body of wash solution. Especially during the winter months when the
detergent composition and water fed to the dispenser are particularly cold,
the detergent viscosity increases markedly Pnd a gel forms. As a result
some of the composition is not flushed completely off the dispenser during
operation of the machine, and a deposit of the composition builds up with
repeated wash cycles, eventually requiring the user to flush the dispenser
with hot water.
The gelling phenomenon can also be a problem whenever it is desired to
carry out washing using cold water as may be recommended for certain
synthetic and delicate ~abrics or fabrics which can shrink in warm or hot
water.
The tendency of concentrated detergent compositions to gel during
storage is aggrevated by storing the compositions in unheated storage areas,
or by shipping the composition~ during winter months in unheRted
2 0 transportation vehicles .
Partial s~lutions to the gelling problem have been proposed, for
example, by diluting the liquid nonionic with certain viscosity controlling
solvents and gel-inhibiting agents, such as lower alkanols, e.g. ethyl alcohol
(see U.S.P. 3,953,380), alkali metal formates and adipates (see U.S.P.
4,368,147), hexylene glycol, polyethylene glycol, etc. and nonionic structure
modification and optimization. As an example of nonionic surfactant
modification one particularly successful result has been achieved by
acidifying the hydroxyl moiety end group of the nonionic molecule. The
advantages of introducing a carboxylic acid at the end of the nonionic
include gel inhibition upon dilution: decreasing the nonionic pour point; and
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~2~3~9 62301-1391
formation of an anionic surfactant when neutralized in the
washing liquor. Nonionic structure optimization has centered
on the chain length of the hydrophobic-lipophilic moiety and
the nurnber and make-up of alkylene oxide (e.g. ethylene oxide)
units of the hydrophilic moiety. For example, it has been
found that a C13 fatty alcohol ethoxylated with 8 moles of
ethylene oxide presents only a limited tendency to gel
formation.
Nevertheless, improvements are desired in both the
stability and gel inhibition of nonaqueous liquid fabric
treating compositions.
BRIEF DESCRIPTION OF THE INVENTION
In accordance with the present invention there is
provided a non-aqueous fabric treating detergent composition
which comprises a suspension of insoluble inorganic builder
salt particles in 10 to 60 percent of a non-ionic liquid
surfactant detergent, and 0.1 to 5% of an urea compound anti-
settling agent to increase the stability of the suspension.
The compositions of the present invention contain as
an es~ential ingredient urea anti-settling stabilizing
additive. The urea anti-settling stabilizing additive is
believed to function in the detergent composition as a surface
active agent to make the phosphate detergent builder more
compatible with the nonionic surfactant detergent.
The urea is believed to interact with the anionic
phosphate detergent builder salts to make the builder salts
more compatible with the nonionic surEactant and improve -the
contact between the bui:Lder salts and nonionic surfactant. The
improvement in the contact between the phosphate and nonionic
surfactant increases the s-tability of the phosphate suspension
in the nonionic surface active agent.
12683~3~
62301-1391
The urea compound even when added to the composition
in small amounts lmproves the dispersibility of the suspension
of builder salt by acting to inhibit gel formation of the
suspension of builder salt.
The urea improves dispersibility by inhibiting gel
formation of the suspension of detergent builder salt particles
when water is added to the composition, for example, in the
dispensing drawer of a dishwashing machine and/or when the
composition is added to water.
The urea compound that is used in the compositions of
the present invention has the formula H2NCONH2. The urea Eorms
a tautomer which has the ~ormula H2NCNHOH and is called
carbamide.
In order to improve the viscosity characteristics of
the composition an acid terminated nonionic surfactant can be
added. To further improve the viscosity characteristics of the
composition and the storage properties of the composition there
can be added to the composition viscosity improving and anti
gel agents such alkylene glycol mono alkyl ethers and
a~ditional anti settling agents such as phosphoric acid ester.
In preferred embodiment of the invention the detergent
composition contains an acid terminated nonionic surfactant, an
alkylene glycol mono alkyl ether and urea anti-settling
stabilizing agent.
Sanitizing or bleaching agents and activators
therefor can be added to improve the bleaching and cleansing
characteristics oE the composition.
In an embodiment oE the invention the builder
components of the composition are ground to a particle size of
less than lO0 microns and to preferably less than lO microns to
Eurther improve the stability of the suspension of the builder
~ 2 ~ ~ 3 ~ g 62301-1391
components in the liquid nonionic surfactant detergent.
In addition other ingredients can be added to the
composition such as anti-incrustation agents, anti-foam agents,
optical brighteners, enzymes, anti-redeposition agents, perfume
and dyes.
The presently manufactured washing machines for home
use normally operate at washing temperatures of up to 90C.
About 5 gallons (20 liters) of water are used during the wash
and rinse cycles.
About 200 to 250 gms of powder detergent per wash is
normally used.
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~!33~39
In accordance with the present invention where the concentratèd liquid
detergent is used normally only 100 gms (78 cc) of the liquid detergent
composition is required to wash a full load of dirty laundry.
Accordingly, in one aspect the present invention provides a liquid
5heavy duty laundry composition composed of 8 suspension of Q detergent
builder salt, e. g. a phosphate builder salt, in a liquid nonionic surfactant
wherein the composition includes an effective amount of urea compound to
increase the stability of the suspension against settling and the dispersibilityof the suspension in water.
10According to another aspect, the invention provides a concentrated
liquid heavy duty laundry detergent composition which is stable, non-settling
in storage and non-gelling in storage and in use. The liquid compositions of
the present invention are easily pourable, easily measured and easily put
into the washing machine and are readily dispersible in water.
15According to another aspect, the invention provides a method for
dispensing a liqliid nonionic laundry detergent eomposition into and/or with
cold water without undergoing gelation. In particular, a method is provided
for filling a contsiner with a nonaqueous liquid laundry detergent composition
in which the detergent is eomposed, at least predominantly, of a liquid
20nonionic surface active agent and for dispensing the composition from the
container into an aqueous wash bath, wherein the dispensing is effected by
directin g a stream of unheated water onto the composition such that the
composition is carried by the stream of water into the wash bath.
ADVANTAGES OVER THE PRIOR ART
25The addition of the urea compound to t~e detergent compositions reduce
the problem of dispersed particle settling and phase separation and improves
the dispersibility of the suspended detergent particles in water.
The concentrated nonaqueous liquid nonionic surfactant laundry
detergent compositions of the present invention have the advantages of being
~i~33~3 ~
stable, non-settling in storage, and non-gell;ng in storage. The liquid
compositions are easily pourable, easily measured and easily put into the
laundry washing machines ~nd are readily dispersible in water.
OBJECTS OF THE INVENTION
It is an object of the present invention to pro~ride a stable liquid heavy
duty nonaqueous nonionic detergent composition containing at least one urea
compound anti-settling stabilizing agent and option~lly an anionic phosphate
detergent builder salt suspended in a nonionic surfactant.
It is an other object of the invention to provide liquid fabric treating
compositions which are suspensions of insoluble inorganic particles in a
nonaqueous liquid and which are storage stable, easily pourable and
dispersible in cold, warm or hot water.
Another object of this invention is to formulate highly built heavy duty
nonaqueous liqui~ nonionic surfactant laundry detergent compositionR which
can be poured at all temperatures and which can be repeatedly dispersed
from the dispensing unit of European style automatic laundry washing
mach;nes without Iouling or plugging of the dispenser even during the
winter months.
A specific object of this invention is to provide non-gelling, stable
2 0 suspension~ of heavy duty built nonaqueous liquid nonionic laundry
detergent composition which include an effective amount of a urea compound
which is sufficient to increase the yield stress of the composition to thereby
increase its stability , i. e . prevent settling of builder particles ~ etc .,
preferably while reducing or at least without increasing, the plastic viscosity
(viscosity ùnder shear conditions~ of the composition.
These and other objects of the invention which will become more
apparent from the following detailed description of preferred embodiments are
generally provided for by preparing a detergent composition by adding to
the nonaqueous liquid nonionic surfactant an effective amount of urea
compound anti-settling stabilizing agent suf~icient to inhibit settling of the
~L2683~39
suspended particles, wherein said composition includes inorganic or organic
fabric treating additives, e. g. viscosity improving agents and one or more
anti-gel agents, anti-incrustation agents, pH control agents, bleaching
agents, bleach activators, anti-foam agents, optical brighteners, enzymes,
anti-redeposition agents, perfume, dyes and coloring pigments.
DETAILED DESCRIPTION OF THE INV3~NTION
In accordance with the present invention the physical stability of the
suspension of the anionic phosphate detergent builder compound or
compounds and any other suspended additive, such ~s bleaching agent, etc~
in the liquid nonionic surfactant vehicle is substantially improved by the
addition of an anti-~ettling stabiilzing agent which i~ urea.
The addition of very small amounts OI the urea anti-settling stabilizing
agent is sufficient to substantially improve the physical stability of the
detergent compositions and the dispersibility of the compositions in water.
The compositis~ns of the present invention contain as an essential
ingredient urea anti-settling stabilizing agent additive. The anti-settling
stabilizing additive can comprise one or more urea compourlds.
Although applicants do not wish to be bound by any particular theory
of the manner by which the urea or carbamide compounds function to
prevent settling of the suspended anionic phosphate builder detergent
particles, it is believed that the urea or carbamide compounds interact with
the anionic phosphate detergent builder salts to make the phosphate more
compatible with the nonionic surfactant, improYe the contact between the
phosphate and nonionic surfactant and inzrease the wettability of the
dispersed phosphate solid particles surIaces by the nonionic surfactant. The
improvement in the contact between the phosphate and nonionic surfactant
and the improved wettability of the dispersed phosphate particles by the
nonionic surfactant increases the stability of the phosphate suspension and
allows the suspended phosphate to more easily remain in suspension.
~L2~
The urea is believed to interact with the anionic pho~phate detergent
builder salts to make the builder salts more compatible with the nonionic
surfactant and improve the contact between the builder salt6 and nonionic
surfactant. The improvement in the contact between the phosphate and
nonionic surfactant increases the stability of the phosphate suspension in the
nonionic surface active agent.
The increased physical stability is manifested by an increase in the
yield stress of the composition as compared to the same composition without
the stabilizing agent. As described above, the higher is the yield stress,
the higher is the apparent viscosity at low shear rate and the better is the
physical stability.
The urea compound even when added to the composition in small
amounts improves the dispersibility of the suspension of builder salt by
acting to inhibit gel formation of the ~uspension of builder when contacted
with water.
The urea improves dispersibility by inhibiting gel formation of the
suspension of detergent buil~ler salt particles when water is added to the
composition, for example, in the dispensing drawer of a dishwashing mRchine
and/or when the composition i8 added to the wash water.
2 0 The urea compounds that are u6ed in the compositions of the present
invention have the formula RlR2NCNR3R4
X
wherein at least one of the R1 to R4 is hydrogen and the remainder are
alkyl, preferably Cl to C4 alkyl, aryl, preferably phenyl, hydroxyl or
chlorine, and X i8 0 or NH. The urea ~orms a tautomer which has the
formula H2NCNHOH and is called carbamide. Urea and carbamide compounds
and derivative compounds such as methyl urea, dimethyl urea, ethyl urea,
propyl urea, butyl urea, hydroxyl urea and phenyl urea, salts of the
~oregoing are suitable for use in the present invention.
In addition to the action as a physical stabilizing agent, the urea
compounds have the advantages over other physical stabilizing agents that
~ i8;3~3~
they are compatible with the nonionic surfact~nt component and that they
~ubstantially improve the dispensibility of the detergent composition in cold
water.
Only very small amounts of urea compound are required to obtain the
signif;cant improvements in physical stability of the detergent composition,
and the dispersibility of the composition in cold water. For example, based
on the total weight of the nonionic liquid surfactant composition, suitable
amounts of urea are in the range of from about 0.196 to about 5%, preferably
from about 0.2% to about 2.0% and more preferably about 0.5 to 1.5%.
While the urea compounds are effective in their physical stabilizing
action, there can be added to the formulation other known physical
stabilizers, such as, for example, an acidic organic phosphorus compound
having an acidic ~ POH group ~ such as a partial ester of phosphorous acid
and an alkanol.
Nonionic Surfactant Detergent
The nonionic synthetic organic detergents employed in the practice of
the invention may be any of a wide variety of known compounds.
As is well known, the nonionic synthetic organic detergents are
characterized by the presence of an organic hydrophobic group and an
org~nic hydrophilic group and are typically produced by the conden6ation of
an organic aliphatic or alkyl aromatic hydrophobic compound with ethylene
oxide (hydrophilic in nature). Practically any hydrophobic compound having
a carboxy, hydroxy, amido or amino group with a free hydrogen attached to
the nitrogen can be condensed with ethylene oxide or with the polyhydration
product thereof, polyethylene glycol, to ~orm a nonionic detergen$. The
length of the hydrophilic or polyoxy ethylene chain can be readily adjusted
to achieve the desired balance between the hydrophobic and hyd:rophilic
groups . Typical suitable nonionic surfactant~ are those disclosed in U. S .
patents 4,31~,812 and 3,630,929.
Usually, the nonionic detergents are poly-lower alkoxylated lipophiles
wherein the desired hyclrophile-lipophile balance is obtained from addition of
~26~33~
a hydrophilic poly-lower alkoxy group to a lipophilic moiety. A preferred
clAss of the nonionic detergent employed i~ the poly-lower alkoxylated higher
alkanol wherein the alkanol is of 9 to 18 carbon atoms and wherein the
number of mol~ of lower alkylene oxide (of 2 or 3 carbon atoms) is from 3 to
12. t)f such materials it i8 preferred to employ those wherein the higher
alkanol is a higher fatty alcohol of 9 to 11 or 12 to 15 carbon atoms ~nd
which contain from 5 to 8 or 5 to ~ lower alkoxy groups per mol.
Preferably, tlhe lower ~lkoxy i8 ethoxy but in some instances, it may be
desirably mixed with propoxy, the latter, if present, often being a minor
(less thsn 50%) proportion.
Exemplary of such compounds are those wherein the alkanol is of 12 to
15 carbon atoms and which contain nbout 7 ethylene oxide groups per mol,
e . g. Neodol 25-7 and Neodol 23-6 . 5, which products are made by Sh~
Chemical Company, Inc. The former is a condensation product of a mixture
of higher fatty alcohols averaging about 12 to 15 carbon atoms, with about 7
mols of ethylene oxide and the latter is a corresponding mixture wherein the
carbon atom content of the higher fatty alcohol is 12 to 13 and the number
of ethylene oxide groups present averages about 6 . 5 . The higher alcohols
are pr~mary alkanols.
Other examples of such detergents include Tergitol 15-S-7 and Tergitol~
15-S-9, both of which are linear secondary alcohol ethoxylates made by
Union Carbide Corp. The former is mixed ethoxylation product of 11 to 15
carbon atoms linear secondary alkanol with seven mols of ethylene oxide and
the latter is a similar product but with nine mols of ethylene oxide being
2 5 reacted .
Also useful in the present composition as a component of the nonionic
detergent are higher molecular weight nonionics, such a~ Neodol 45-11,
which are similar ethylene oxide condensation products of higher fatty
alcohols, with the higher fatty alcohol being o~ 14 to 15 carbon atoms and
gL~i83;t3~3
the number of ethylene oxide groups per mol being about 11. Such products
are also made by Shell Chemical Company.
Other useful nonionics are represented by the commercially well known
clas~ of noalionics æold under the trademark Plurafac. The Plurafacs are the
reaction product of a higher linear alcohol and a mixture of ethylene and
propylene oxides, containing a mixed chain OI ethylene oxide and propylene
oxide, terminated by a hydroxyl group. Examples include products which
are (A) C13-C15 fatty alcohol condensed with 6 moles ethylene oxide and 3
moles propylene oxide, (B) C13-C15 fatty alcohol condensed with 7 moles
propylene oxide and 4 moles ethylene oxide, (C) C13-C15 fatty alcoh~l
condensed with 5 moles propylene oxide and 10 moles ethylens oxide, and
(D) which is a 1:1 mixture of products (B) snd (C).
Another group of liquid nonionics are commercially available from Shell
Chemical Company, Inc. under the Dobanol trademark: Dobanol 91-5 is an
ethoxylated Cg-C11 fatty alcohol with an average of S moles ethylene oxide
and Dobanol 25-7 is an ethoxylated C12-C15 fatty alcohol with an average of
7 moles ethylene oxide per mole of fatty alcohol.
In the preferred poly-lower alkoxylated higher ~lkanols, to obtain the
best balance of hydrophilic and lipophilic moieties the number of lower
2 0 alkoxies will usually be from 40% to 10096 of the number of carbon atoms in
the higher alcohol, preferably 40 to 60% thereof and the ~lonionic detergent
will preferably contain at least 5096 of such preferred poly-lower alkoxy
higher alkanol. Higher molecular weight alkanols and various other normally
solid nonionic detergents and surface active agents may be contributory to
gelation of the liquid detergent and consequently, will preferably be omitted
or limited in quantity in the present compositions, although minor
proportions thereof may be employed for their cleaning properties, etc. With
respect to both preferred and less preferred nonionic detergents the alkyl
groups present therein are generally linear although branching may be
~i83~
tolerated, such as at a carbon next to or two carbon6 removed from the
terminal carbon of the straight chain and awny from the ethoxy chain, lf
such br~nched Qlkyl i8 not more than three carbon8 in length. Normally,
the proportion of carbon ~toms In 6uch a branched configuration will be
minor rarely exceeding 20% of the totfll carbon atom content of the alkyl,
Similarly, although line~r elkyl~ which are terminally ~olned to the ethylene
oxide chains are highly preferred and are considered to result in the best
combination of detergency, biodegr~dability and non-gelling charscteristics,
medial or secondary joinder ~o the ethylene oxide in the ch~n msy occur. It
0 i6 usually in only a minor propor~ion of such alkylfi, generally less than 20%
bu~, as is in the case~ of the mentioned l~rgitols, may be greater. Al80J
when propylene oxide iB present in the lower ~lkylene oxide chain, it will
usually be les6 than 20% thereof and prefernbly less than lO% thereof
When greater proportions of non-terminally alkoxylated ~Ikanols,
propylene oxide-contEining poly-lower alkoxylated alkanols ~nd les~
hydrophile-lipophile bal~ced nonionic detergent than mentioned ~bo~e are
employed and when other nonionic detergents are used instead of the
preferred nonionics recited herein, the product resulting may not h~e ~
good detergency, stability, vi6c06ity and non-gelling propertie~ Q8 the
preferred compositions but use of the vi~cosity snd gel controlllng
compounds of the invention can al~o lmprove the propertie~ of the deeersents
ba~ed on snch nonionics. In some ca6es, as when a higher molecular weight
polylower alXoxylated higher alXanol is employed, often for its detergency,
the proportion thereof will be regulated or limited in accordance with the
results of routine experiment~, to obtain the desired detergency and still
have the product non-gelling and of desired viscosity. Also, it has been
found that it i8 only rarely necessary to utilize the higher molecular wei~ht
nonionics for their detergent properties since the preferred nonionics
described hereirl are excellent detergents and ~ddiffonally, per-lt the
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~83~ 62301-1391
attainment oE the desired vlscosity in the liquid detergent
without gelation at low temperatures.
Another useEul group of nonionic surfactants are the
"Surfactant T" series of nonionics available from British
Petroleum. The Surfactant T nonionics are obtained by the
ethoxylation of secondary C13 fatty alcohols having a narrow
ethylene oxide distribution. The Surfactant T5 has an average
of 5 moles of ethylene oxide; Surfactant T7 an average of 7
moles of ethylene oxide; Surfactant T9 an average of 9 moles of
ethylene oxide and Surfactant T12 an average of 12 moles of
ethylene oxide per mole of secondary C13 fatty alcohol.
In the compositions of this invention, preferred
nonionic surfactants include the C12-C15 secondary fatty
alcohols with relatively narrow contents of ethylene oxide in
the range of from about 7 to 9 moles, and the C9 to Cll fatty
alcohols ethoxylated with about 5-6 moles ethylene oxide.
Mixtures of two or more of the liquld nonionic
surfactants can be used and in some cases advantages can be
obtained by the use of such mixtures.
Acid Terminated Nonionic Surfactant
The ~iscosity and gel properties of the liquid
detergent compositions can be improved by includin~ in the
composition an effective amount of an acid termina-ted liquid
nonionic surfactant. The acid terminated nonionic surfactants
consist of a nonionic surfactant which has been modified to
convert a free hydroxyl group thereof to a moiety having a free
carboxyl group, such as an ester or a partial ester of a
nonionic surfactant and a polycarboxylic acid or anhydride.
16
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~6~3~ 62301-1391
As disclosed in the commonly assigned Canadian
application No. 478,379, filed April 4th, 1985, the free
carboxyl group modiEied nonionic surfactants, which may be
broadly characterized as polyether carboxylic acids, function
to lower the temperature at which the liquid nonionic forms a
gel with water.
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The addition of the acid terminated nonionic surfsctants to the liquid
nonionic surfactant aids in the dispensibi]ity of the composition, i.e.
pourability, and lowers the temperature at which the liquid nonionic
surfactants form a gel in water without a decrease in their ~tability against
settling. The acid terminated nonion~c surfactant reacts in the washing
machine water with the alkalinity OI the dispersed builder salt phase of the
detergent composition and acts as an effective anionic surfactant.
Specific examples include the half-ester~ OI product (A) with succinic
anhydride, the ester or half ester of Doballol 25-7 with succinic anhydride,
and the ester or half ester of Dolbanol 91-5 with succinic anhydride. Instead
of succinic anhydride, other polycarboxylic acids or anhydrides can be used,
e. g. maleic acid, maleic acid anhydride, ghltaric acid, malonic acid, phthalic
acid, phthalic anhydride, citric acid and the like.
The acid terminated nonionic surfactants can be prepared as followR:
Acid Terminated product (A). 400g of product (A) nonionic surfactant
which is a C13 to C15 alkanol which has been alkoxylated to introduce 6
ethylene oxide ~nd 3 propylene oxide units per alkanol uni$ is mixed with
32g of succinic anhydride and heated for 7 ho~rs at 100C. The mixture i8
cooled and filtered to remove unreacted succinic material. Infrared analysis
2 0 indicated that about one hal of the nonionic surfactant has been converted
to the acidic half-ester thereof.
Acid Terminated Dobanol 25-7. 522g of Dobanol 25-7 nonionic
surfactant wh;ch is the product of ethoxylation of a C12 to C15 alkanol and
has about 7 ethylene oxide units per molecule of alkanol is mixed with 100g
of succinic anhydride and 0. lg of pyridine (which acts as an esterification
catalyst) and heated at 260C for ~ hour6, cooled and filtered to remove
unreacted succinic material. Infrared analy~is indicates that substantially all
the free hydroxyls of the surfactant have reacted.
Acid Terminate Dobanol gl-5. 1000 of Dobanol 91-5 nonionic surfactant
which is the product of ethoxylation of a Cg to C:l1 alkanol and has about 5
~ 338~ `
ethylene oxide units per molecule of alkanol is mixed with 265g of succinic
anhydride and O.lg of pyridine catalyst and hested at 260C for 2 hour~,
cooled and filtered to remove unreacted succinic material. Infrared analysis
indicates that substantially all the free hydroxyls of the surfactant have
reacted .
Other esterif;cation catalysts, such as an alkali metal allcoxide (e. g.
sodium methoxide) may be used in place of, or in admixture with, the
py~dine .
The acidic polyether compound, i . e . the acid terminated nonionic
surfactant is preferably added dissolved in the nonionic sur~actant.
BUILDER SALTS
The liquid nonaqueous nonic~nic surfactant used in the compositions of
the present invention has dispersed and suspended therein fine particles of
inorganic and/or inorganic detergent builder salts.
The invention detergent compositions include water soluble and/or water
insoluble detergent builder salts. Water soluble inorganic alkaline builder
salt~ which can be used alone with the detergent compound or in admixture
with other builders are alkali metal carbonates, bicarbonates, borates,
phosphates, polyphosphates, and silicates. (Ammoniurn or substituted
ammonium salt6 can also be used. ) Specific examples of such s~lt~ are
sodium tripolyphosphate, sodium carbonate, sodium tetraborate, sodium
pyrophosphate, potassium pyrophosphate, sodiurn bicarbonate, potassium
tripolyphosphate, sodium hexametaphosphate, sodium sesquicarbonate ~ sodium
mono and diorthophosphate; and potassium bicarbonate. Sodium
tripolyphosphate ~TPP) is especially preferred.
Since the compositions of this invention are generally highly
concentrated, and, therefore, rnay be used at relatively low dosages, it is
desirable to supplement any phosphate builder (such as sodium
tripolyphosphate) with an au~liary builder such as a poly lower carboxylic
acid or a polymeric carboxylic acid having high calcium binding capacity to
~ 6~138~ .
inhibit incrustation which could otherwi~e be caused by formation of an
insoluble calcium phosphate.
A suitable lower poly carboxylic acid comprises alkali metal salts of
lower polycarboxylic acids, preferably the sodium and potassium salts.
Suitable lower polycarboxylic acids have two to four carboxylic acid groups.
The preferred sodium and potassium lower polycarboxylic acids salts are the
citric and tsrtaric acid salts.
The sodium citric acid salts are the most preferred, especinlly the
trisodium citrate. The monosodium and disodium citrate6 can also be used.
The monosodium and disodium tartaric acid salts can also be usedO The
alkali metal lower polycarboxylic acid salts are particularly good builder
salts; because of their high ealcium and magnes;um binding capacity they
inhibit incrustation which could otherrnse be caused by formation of insoluble
calcium and magnesium s~lts.
Other organic builders are polymers and copolymers of polyacrylic acid
and polymaleie anhydride and the alkali metal salts thereof. More ~pecifically
such b-~ilder salts can consist of a copolymer which i8 the reaction product
of about equal moles of methacrylic acid and maleic anhydride which has been
completely neutralized to form the sodium salt thereof. The builder i6
2 0 commercially available under the tradename of Sokalan CP5 . This builder
serves when used even in small amounts to inhibit incrustation.
Example6 of organic alkaline seques$rflnt builder salts which can be
used with the detergent builder salts or in admixture with other organic and
inorganic builders are alkali metal, ammonium or substituted ammonium,
aminopolycarboxylates, e. g. sodium and potassium ethylene
diaminetetraacetate (EDTA~, sodium and potassium nitrilotriacetates ~NTA),
and triethanolammonium N-(2-hydroxyethyl)nitrilodiace$ates. Mixed salts of
these aminopolycarboxylates are also suitable.
Other suitable bullders of the organic type include
carboxymethylsuccinates, tartronates and glycollates. Of special value are
~L26~38~
62301-1391
the polyacetal carboxylates. The polyacetal carboxylates and
their use in detergent compositions are described in Canadian
application No. 516,256, filed ~ugust l9th, 1986 assigned to
applicants' assignee and in a U.S.P. Nos. 4,144,226, 4,315,092
and 4,146,495.
The alkali metal silicates are useful builder salts
which also function to adjust or control the pH and to make the
composition anticorrosive to washing machine parts. Sodium
silicates of Na2O/SiO2 ratios of from 1.6/1 to 1/3.2,
especially about 1/2 to 1/2.8 are preferred. Potassium
silicates of the same ratios can also be used.
Other typical suitable builders include, for example
those disclosed in U~S. Patents 4,316,812, 4,264,466 and
3,630,929. The inorganic builder salts can be used with thé
nonionic surfactant detergent compound or in admixture with
other inorganic builder salts or with,organic builder salts.
The water insoluble crystalline and amorphous
aluminosilicate zeolites can be used. The zeolites generally
h~ve the formula
(M2)x (A123~y (~iO2)~-wH2o
wherein x is 1, y is from 0.8 to 1.2 and preferably 1, z is
from 1.5 to 3.5 or higher and preferably 2 to 3 and w is from 0
to 9, preferably 2.5 to 6 and M is preferably sodium. A
typical zeolite is type A or similar structure, with type 4A
particularly preferred. The preferred aluminosilicates have
calcium ion exchange capacities of about 200 milliequivalents
per gram or greater, e.g. 400meq lg.
Various crystalline zeolites (i.e. alumino-silicates)
that can be used are described in British Patent 1,504,168,
U.S.P. 4,409,136 and Canadian Patents 1,072,835 and 1,087,477. `
An example of amorphous zeolites useful herein can be found in
, .
~LZ~!3389
62301-1391
Belgium Patent 835,351.
Other materials such as clays, particularly oE the
water-insoluble types, may be useful adjuncts in compositions
of this invention. Particularly useful is bentonite. This
material is primarily montmorillonite which is a hydrated
aluminum silicate in which about l/5th of the aluminum atoms
may be replaced by magnesium atoms and with which varying
amounts of hydrogen, sodium, potassium, calcium, etc., may be
loosely combined. The bentonite in its more purified form
(i.e. free from any grit, sand, etc.) suitable for detergents
contains at least 50~ montmorillonite and thus its cation
exchange capacity is at least about 50 to 75 meq per 100g of
bentonite. Particularly preferred bentoni-tes are the ~yoming
or Western U.S. bentonites which have been sold as Thixo-jels
1, 2, 3 and ~ by Georgia Kaolin Co. These bentonites are known
to soften textiles as described in British Patent 401,413 to
Marriott and British Patent ~61,221 to Marriott and Guan.
Viscosity Control and Anti Gel Aqents
The inclusion in the detergent compositions of an
effective amount of low molecular weight amphiphilic compounds
which function as viscosity control and gel inhibiting agents
for the nonionic surfactant substantially improves the storage
properties of the composition. The viscosity control and gel
inhibiting agents act to lower the temperature at which the
nonionic surEactant will form a gel when added to water. Such
viscosity control and gel inhibiting agents can be, for
example, low molecular weight alkylene oxide lower mono-alkyl
ether amphilic compounds. The amphiphili~ compounds can be
considered to be analagous in chemical structure to the
ethoxylated and/or propoxylated fatty alcohol liquid nonionic
surfactants but have relatively short hydrocarbon chain lengths
:. 't '~
~ ,j
~2683~3~
62301-1391
(C2 to C8) and a low content of ethylene oxide (about 2 to 6
ethylene oxide groups per molecule). Suitable amphiphilic
compounds are represented by the following general formula
R O(CH2CH2O)nH
where R is a C2-C8 alkyl group, and n ls a number oE
from about 1 to 6, on average.
Specifically the compounds are lower (C2 to C3)
alkylene glycol mono lower (C2 to C5) alkyl ethers.
More specifically the compounds are mono di- or trl
lower (C2 to C3) alkylene glycol mono lower (Cl to C5) alkyl
ethers.
Specific examples of suitable amphiphilic compounds
include ethylene glycol monoethyl ether C2H5-O-CH2CH2OH,
diethylene glycol monobutyl ether C4Hg-O-(CH2CH2O)2H,
tetraethylene glycol monobutyl ether C4H7-O-(CH2CH2O)4H, and
dipropylene glycol monomethyl ether CH3-O-(CHCH2O)2H.
CH3
Diethylene glycol monobutyl ether is especially preferred.
The inclusion in the composition of the low molecular
weight lower alkylene glycol mono alkyl ether decreases the
viscosity of the composition, such that it is more easily
pourable, improves the stability against settling and improves
the dispersibility of the composition on the addition to warm
water or cold water.
The compositions of the present invention have
improved viscosity and stability characteristics and remain
stable and pourable at temperatures as low as about 5C and
lower.
The urea compounds in addition to acting as an anti-
settling stabilizing agent acts to improve the dispersibility
of the suspension of phosphate detergent builder particles by
':
1~61~33~3
62301-1391
inhibiting gel formation of the suspended particles when co]d
water i5 added to the composition in the dispensing drawer
and/or when the composition is added to water~
In an embodiment of this invention a supplemental
stabilizing agent which is an alkanol ester of phosphoric acid
can be added to the formulation. Improvements in stability of
the composition may be achieved by incorporation of a small
effective amount of an acidic organic phosphorus compound
having an acidic - POH group, such as a partial ester of
phosphorus acid and an alkanol~
As disclosed in the commonly assigned copending
Canadian application No. 478,379, filed April 4th, 1985, the
acidic organic phosphorous compound having an acidic - POH
group can increase the stability of the suspension oE the
suspension of builders in the nonaqueous liquid nonionic
surfactantO
The acidic organic phosphorus compound may be, for
instance, a partial ester of phosphoric acid and an alcohol
such as an alkanol which has a lipophilic character, having,
; 20 for instance, more than 5 carbon atoms, e.g. 8 to 20 carbon
atoms.
A specific example is a partial ester oE phosphoric
acid and a C16 to C18 alkanol (Empiphos 5632 from Marchon); it
is made up of about 35% monoester and 65% diester.
The inclusion of quite small amounts of the acidic
organic phosphorus compound makes the suspension stable against
settling on standing but remains pourable, while, Eor the low
concentration oE stabilizer, e.g~ be]ow about 1%~ its plastic
viscosity will generally decrease.
Bleachina Aaents
The bleaching agents are classified broadly, for
23
~ 38~ 62301-1391
convenience, as chlorine bleaches and oxygen bleaches.
Chlorine bleaches are typified by sodium hypochlorite (NaOCl),
potassium dichloroisocyanurate (59~ available chlorlne), and
trichloroisocyanuric acid (95~ available chlorine). Oxygen
bleaches are preferred and are represented by percompounds
which liberate hydrogen peroxide in solution. Preferred
examples include sodium and potassium perborates,
percarbonates, and perphosphates, and potassium monopersulfate.
The perborates, particularly sodium perborate monahydrate, are
especially preferred.
The peroxygen compound is preferably used in
admixture with an activator therefor. Suitable activators
which can lower the effective operating temperature of the
peroxide bleaching agent are disclosed, for example, in U.S.P.
4,264,466 or in column 1 of U.S.P. 4,430,244. Polyacylated
compounds are preferred activators; among these, compounds such
as tetraacetyl ethylenediamine ("TAED") and pentaacetyl glucose
are particularly preferred.
Other useful activators include, for example,
acetylsalicylic acid derivatives, ethylidene benzoate acetate
and its salts, ethylidene carboxylate acetate and its salts,
alkyl and alken~l succinic anhydride, tetraacetylglycouril
t"TAGU"), and the derivatives of these. Other useful classes
of activators are disclosed, for example, in U.S.P. 4,111,826,
4,422,950 and 3,661,789.
The bleach activator usually interacts with the
peroxygen compaund to form a peroxyacid bleaching agent in the
wash water. It is preferred to include a sequestering agent of
high complexing power to inhibit any undesired reaction between
such peroxyacid and hydrogen peroxide in the wash solution in
the presence of metal ions.
;~ 24
....
~:
~26~3~ 62301-1391
Suitable sequestering agents Eor this p~rpose include
the sodium salts of nitrilotriace~ic acid (NTA), ethylene
diamine tetraacetic acid (EDTA), diethylene triamine
pentaacetic acid ( DETPA), diethylene triamine pentamethylene
phosphonic acid (DTPMP) sold under the tradename Dequest 2066;
and ethylene diamine tetramethylene phosphonic acid (EDITEMPA).
The sequestering agents can be used alone or in admixture.
In order to avoid loss oE peroxide bleaching agent,
e.g. sodium perborate, resulting from enzyme-induced
decomposition, such as by catalase enzyme, the compositions may
additionally include an enzyme inhibi-tor compound, i.e. a
compound capable of inhibiting enzyme-induced clecomposition of
the peroxide bleaching agent. Suitable inhibitor compounds are
disclosed in U.S.P 3,606,990.
Of special interest as the inhibitor compound,
mention can be made of hydroxylamine sulfate and other water-
soluble hydroxylamine salts. In the preferred nonaqueous
compositions of this invention, suitable amounts of the
h~droxylamine salt inhibitors can be as low as about n . ol to
0~4%O Generally, however, suitable amounts of enzyme
inhibitors are up to about 15%, for example, 0.1 to 10%, by
weight oE the composition.
In addition to the detergent builders, various other
detergent additives or adjuvants may be present in the
detergent product to give it additional desired properties,
either of functional or aesthetic nature. Thus, there may be
included in the formulation, minor amounts o soil suspending
or anti-redeposition agents, e.g. polyvinyl alcohol, fatty
amides, sodium carboxymethyl cellulose, hydroxy-propyl methyl
cellulose. A preferred anti-redeposition agent is sodium
carboxymethyl cellulose having a 2:1 ratio of CMC/MC which is
~LZ~389
62301-1391
sold under the trademark Relation DM 4050.
There may also be included in the composition small
amounts oE an alkyl or alkylene succinic anhydride, such as
octenyl succinic anhydride which functions as a viscosity
control and anti-gel agent. The octenyl succinic anhydride can
be added in amounts such as 0.5 to 10~, preferably 1 to 6%
percent and more preferably 1 to 4% by weight of the
composition.
Optical brighteners for cotton, polyamide and
polyester fabrics can be used. Suitable optical brighteners
include stilbene, triazole and benzidine sulfone compositions,
especially sulfonated substituted triazinyl stilbene,
sulfonated naphthotriazole stilbene, benzidene sulfone, etcO,
most preferred are stilbene and triazole combinations.
En2ymes, preferably proteolytic enzymes, such as
; subtilisin, bromelin, papain, trypsin and pepsin, as well as
amylase type enzymes, lipase type enzymes, and mixtures thereof
can be added. Preferred enzymes include protease slurry,
esperase slurry and amylase. A preferred enzyme is Esperse*
~L8 which is a proteolytic enzyme. Anti-Eoam agents, e.gO
silicon compound, such as Silicane* L 7604, which is
polysiloxane can also be added in small effec-tive amounts.
Bactericides, e.g. tetrachlorosalicylanilide and
hexachlorophene, fungicides, dyes, pigments (water
dispersible), preservatives, ultraviolet absorbers, anti-
yellowing agents, such as sodium carboxymethyl cellulose, pH
modifiers and pH buffers, color saEe bleaches, perfume, and
dyes and bluing agents such as ultramarine blue can be used.
The composition may also contain small amounts of
:
paint pigments to provide coloring such as Tio2 white pigment.
*Trademark
:
~ 25
:~' , ,.
~,
,. ~, .
~ILZ6~33~
62301-1391
The Tio2 can be added in amounts such as 0.1 to ~%, preferably
0.1 to ~% and more preferably 0.1 to 1%.
The composition may also contain an inoryanic
insoluble thickening agent or dispersant of very high surface
area such as finely divided silica of extremely fine particle
size (e.g. of 5-100 millimicrons diameters such as sold under
the trademark Aerosil) or the other highly voluminous inorganic
carrier materials disclosed in U.S.P. 3,630~929, in proportions
of 0.1 - 10%, e.g. 1 to 5%. It is preferable, however, that
compositions which form peroxyacids in the wash bath (e.g.
compositions containing peroxygen compound and activator
therefor) be substantially free of such compounds and of other
silicates; it has been found, for instance, that silica and
silicates promote the undesired decomposition of the
peroxyacid.
In an embodiment of the invention the stability of
the builder salts in the composition during storage and the
dispersibility o~ the composition in water is improved by
grinding and reducing the particle size of the solid builders
; 20 to less than 100 microns, preferably less than 40 microns and
more preferably to less than 10 microns. The solid builders,
e.g. sodium tripolyphosphate (TPP), are generally supplied in
particle sizes of about 100, 200 or 400 microns. The nonionic
liquid surfactant phase can be mixed with the solid builders
prior to or after carrying out the grinding operation.
26a
3L21~;83~3
In a preferred embodiment of the invention, the mixture of liquid
nonionic surfactant and solid ingredients is subjected to an attrition t~pe of
mill in which the particle 6izeS of the solid ingredients are reduced to le6s
than about 10 microns, e.g. to an average particle size of 2 to 10 microns or
even lower (e.g. 1 micron). Preferably less than about 10%, e~pecially less
than about 5% of all the suspended particles have particle sizes greater than
10 microns. Compositions whose dispersed particles are of such small size
have improved stability against separation or settling on storage. Addition
of the acid terminated nonionic surfactant compound can decrease the yield
stres6 of such dispersions and aid in the dispersibility of the dispersions
without a corresponding decrease in the dispersions stability against
settling.
In the grinding operation, it is Rreferred that the proportion of solid
ingredients be high enough (e.g. at least about 40~ such 86 about 50%~ that
the solid particles are in contact with each other and ~re not substantially
shielded from one another by the nonionic surfactant liquid. After the
grinding step any remaining liquid nonionic surfactant ean be added to the
ground formulation. ~ 18 which employ grinding balls ~ball mills~ or similar
mobile grinding element~ have ~en very good results. Thus, one may use
a laboratory b~$ch attritor having 8 mm diameter steatite grinding balls. For
larger scale work a continuously operating mill in which there are 1 mm or
1.5 mm diameter grinding balls working in a very small gap between a stator
and a rotor operating at a relatively high speed (e.g. a C:oBall mill) may be
employed; when using such a mill, it is desirable to pass the blend of
~5 nonionic surfactant and solids first through a mill which doeæ not effect such
~Ine grindin~ (e.g. a colloid mill) to reduce the particle size to le~s than 100microns (e. g. to about 40 microns) prior to the step of grinding to an
average particle diameter below about 10 microns in the continuous ball mill.
~ 3~3a9
In the preferred heavy duty liquid laundry detergent compositions of
the invention, typical proportions (percent based on the total weight of
composition, unless otherwise specified) OI the ingredient6 are as follows:
Liquid nonionic surfactant detergent in the range of about 10 to 60,
5~uch as 20 to 50 percent, e.g. about 30 to 40 percent.
Acid terminated nonionic surfactant in an amount in the range of about
0 to 20, such as 3 to 15 percent, e.g. about 4 to 10.
Detergent builder, such as sodium tripolyphosphate (TPP), in the range
of about 10 to 60, such as 15 to 50 percent, e.g. about 25 to 35.
10Alkali metal silicate in the range of about û to 30, such as 5 to 25
percent, e.g. about 10 to 20.
Copolymer of polyacrylate and polymaleic anhydride alkali metal salt,
e. g. Sokalan CP5, anti-incrustation agent in the range of about 0 to 10,
such as 2 to 8 percent, e.g. about 3 to 5.
15Alkylene glycol monoalkylether anti-gel agent in an amolmt in the range
of about 5 to 3D, ~uch as 5 to 20 percent, e.g. about 5 to 15.
The urea compound added in an amount such a~ 0.1 to 5 percent 9
preferably 0 . 2 to 2 . 0 percent and more preferably 0 . 5 to 1. 5 percent . It is
an e~sential feature ~ the invention that the urea compound be included in
20the composition.
Phosphoric acid alkanol ester stabilizing agent in the range of 0 to 2 . O
or 0.1 to 2.0, ~uch as 0.10 to 1.0 percent.
Bleaching agent in the range of about U to 30, such as 2 to 2Q, e. g.
about 5 to 15 percent.
25Bleach activator in the range of about 0 to 15, such as 1 to 8, e. g.
about 2 to 6 percent.
Sequestering agent ~or bleach, e. g. Dequest 2066, in the range of
about 0 to 3 . 0, preferably 0 . 5 to 2 . 0 percent, e . g. about 0 . 75 to 1. 25
percent~
~i8~
Anti-redeposition agent, e.g. Relatin DM 4050, in the range of about 0
to 4 . 0, preferably 0 . 5 to 3 . 0 percent, e . g. 0 . 5 to 1. 5 percent .
Optical brightener in the range of about 0 to 2 . O, preferably 0. 05 to
1.0 percent, e.g. 0.15 to 0.75 percent.
Enzymes in the range of about 0 tc~ 3.0, preferrably 0.5 to 2.û percent,
e.g. 0.75 to 1.25 percent.
Perfume in the range of about 0 to 3 . 0, preferably 0.10 to 1. 25
percent, e.g. 0.25 to 1.0 percent.
Coloring pigment in the range of about 0.1 to 4.0, preferably 0.1 to
2.0, more preferably 0.1 to 1.0 percent.
Various of the previously mentioned additives can optionally be added to
achieve the desired function of the added materialR.
The urea anti-settling stabilizing agent is preferably use with at least
one of the alkylene glycol mono-ether or the acid terminated nonionic
surfactant viscosity control and anti-gel agents. In some cases advantages
can be obtained by using both the alkylene glycol mono~ethers and the acid
terminated nonionic surfactants.
In the ~election of the ad-litiyes, they will be chosen to be compatible
with the m~in constituent6 of th~ detergent composition. In this application,
as mentioned ~bove, all proportions and percentages are by weight of the
entire formulation or composition unless otherwise indicated~
The concentrated nonaqueous nonionic liquid detergent composition of
the present inventi~n dispenses readily in the water in the washing machine~
The presently used home washing machines normally use 200 to 250 gms of
powder detergent to wash a full load of laundry. ln accordance with the
preqent invention only 78 cc or 100 gms of the concqntrated liquid nonionic
detergent composition is needed.
~ "
~Z~3~9
62301-1391
In an embodiment oE the invention the detergent
composition of a typical Eormulation is formulated using the
below named ingredients:
Weiaht %
Nonionic surfactant detergent. 30 - 40
Acid terminated surfactant. 0 - 20
Phosphate detergent builder salt.10 - 60
Anti-incrustation agent. 0 - 10
Alkylene glycol monoalkylether anti-gel agent. 5 - 15
Urea compound. 0.2 - 2~0
Anti-redeposition agent. 0 - 4.0
Alkali metal perborate bleaching agent. 5 - 15
Bleach activator (TAED). 1.0 - 8.0
Sequestering agent for bleach. 0 - 3.0
Optical brightener. 0~05 - 0.75
Enzymes. 0.75 - 1.25
Perfume. 0.1 - 1.0
A preferred embodimen-t comprises:
Weiqht %
Nonionic surfactant in an amount of about 20 - 50
Sodium Tri polyphosphate (TPP) in an amount of about 15 - 50
Copolymer of methacrylic acid and maleic anhydride
sodium salt in an amount of about 2 - 8
Diethylene glycol Cl -to C5 mono alkyl ether
in an amount of about 5 - 20
Urea in an amount of about 0.2 - 2.0
Sodium perborate monohydrate bleaching/agent in an
àmount oE about 2 - 20
Tetraacetylethylene diamine (TEAD) in an
amount oE about 1 - 10.
i ~ .
~ ~ .
~ 3~ 62301~1391
A particularly preferrecl embodiment comprises:
Welaht
Nonionic surfactan-t in an amount of about 30 - 40
Octenyl succinic anhydride in an amount of about 1 - 6
Sodium tripolyphosphate in an amount of about 25 - 35
Copolymer of methacrylic acid and maleic
anhydride sodium salt in an amount o~ about 3 - 5
Diethylene glycol monobutylether in an amoun-t
of about 5 - 15
~rea in an amount of about 0.5 - 1.5
Sodlum perborate monohydrate bleaching agent in an
amount of about 5 - 15
Tetraacetylethylene diamine (TAED) bleach activator
in an amount of about 2 - 6.0
Anti-redeposition agent in an amount of about 0.5 - 1.5.
30a
. .
i2G83a9
The present invention is further illustrated by the following examples.
EXAMPLE 1
A concentrated nonaqueous liquid nonionic surfactant detergent
composition is formulated from the following ingredients in the amounts
specified .
Weight %
Nonionic surfactant . 37 . ?
Acid terminated Dobanol 91-5 reaction product with 5.0
succinic anhydride.
Sodium tri polyphosphate (TPP~. 30
Diethylene glycol monobutylether antî-gel agent. 10
Urea . 1. 0
Sodium perborate monohydrate bleaehing agent. 9.0
Tetraacetylethylene diamine (TAED) bleach activator. 4.5
Anti-redeposition agent (Relatin DM 4096)(13 1.0
Optical brightener~ 0.2
PerfwDe . O . 6
Enzyme ~which is Esperase). 1,0
~1) CMC/MG 2:1 mixture OI sodium carboxymethyl cellulose and
2 0 hydrosymethylcellulose .
The addition of 1% of urea is found to increase the yield stress of the
formulation .
The ~ormulation is ground for about 1.0 hour to reduce the particle size
; of the suspended builder salts to less than 1, 0 microns . The formulated
detergent composition is found to be stable and non-gelling in storage and
readily dispersible in water.
~z~a~ -
EXAMPLE 2
A concentrated nonaqueous liquid nonionic surfactant detergent
composition is formulated from the following ingredients in the amounts
specified .
Weight %
Surfactant T7. 18
Surfactant T9. 18
Octenyl succinic anhydride . 2
Sodium tri-polyphosphate (TPP). 29.5
Anti-incrustation agent (Sokalan CP5). ~.0
Diethylene glycol monobutylether anti gel agent. 10
Urea anti-settling stabilizing agent. 1.0
Sodium perborate monohydriate bleaching agent. 9
Tetraacetylethylene diamine ~TAED) bleaching agent. 4.5
Sequestering agent for bleach (Dequest 2066). 1.0
Anti-redeposition agent (Relatin DM 9096)(2). 1.0
Optical brighteners ~ATS-X). 0.2
Enzyme (which is a protea~e). 1~0
Perfume . ~
TiO2 (pigment). 0.2
(1) Viscosity control and anti-gel agent.
(2) CMC/MC 2 :1 mixture of sodium carboxymethyl cellulose and
hydroxymethylcellulose .
The addition OI 1 percent of urea is found to increase the yield stress
of the formulation. The apparent viscosity o~ the formulation at 100
reciprocal seconds is found to be 1.1 Pa.
The formulation is ground for about 1 hour to reduce the particle slze
of the suspended builder salts to less than 10 microns. The formulated
detergent composition is found to be stable and ncm-gelling in storage and
readily dispersible in water.
The formulations Df Examples 1 and 2 can be prepared without grinding
the builder salts and suspended solid particles to a small particle size, but
. .
~2~;~3313~
best results are obtained by grinding the formulation to reduce the particle
size of the suspended solid particles.
The builder salts can be used us provided or the builder salts and
suspended solid particles can be ground or partially ground prior to mixing
them with the nonionic surfactant. The grinding can be carried out in part
prior to mixing and grinding completed a~er mixing or the entire grinding
operation can be carried out after mixing with the liquid surfactant. The
formulations containing suspended builder and solid particles les6 than 10
microns in size are preferred.
The urea anti-settling stabilizing agent can also be used to improve the
compatibility of the nonionic surfactant and polyphosphate detergent builder
salt in powder detergent compositions.
It is understood that the foregoing detailed description is given merely
by way of illustration and that variations may be made therein without
departing from the spirit of the invention.
